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The organometallic chemistry of the transition metals /
Fully updated and expanded to reflect recent advances, the sixth edition of this bestselling text provides students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction...
| Clasificación: | Libro Electrónico |
|---|---|
| Autor principal: | |
| Formato: | Electrónico eBook |
| Idioma: | Inglés |
| Publicado: |
Hoboken, New Jersey :
Wiley,
[2014]
|
| Edición: | Sixth edition. |
| Temas: | |
| Acceso en línea: | Texto completo |
Tabla de Contenidos:
- 9.3 Hydrogenation
- Oxidative Addition Pathway
- Directing Effects
- Asymmetric Catalysis
- Reversibility
- Heterolytic H2 Activation
- Homolytic H2 Activation
- Outer Sphere Hydrogenation
- Transfer Hydrogenation
- Nanoparticles
- 9.4 Alkene Hydroformylation
- Chelating and Phosphite Ligands
- 9.5 Alkene Hydrocyanation
- 9.6 Alkene Hydrosilylation and Hydroboration
- Hydrosilylation
- Hydroboration
- 9.7 Coupling Reactions
- 9.8 Organometallic Oxidation Catalysis
- Oxidase Reactions
- Water Splitting and C-H Oxidation
- 9.9 Surface, Supported, and Cooperative Catalysis
- Surface Organometallic Chemistry
- Cooperative Catalysis
- Hidden Acid Catalysis
- References
- Problems
- 10: Physical Methods
- 10.1 Isolation
- 10.2 1H NMR Spectroscopy
- Virtual Coupling
- Diastereotopy
- Chemical Shifts
- Paramagnetic NMR
- 10.3 13C NMR Spectroscopy
- 10.4 31P NMR Spectroscopy
- Mechanistic Study of Wilkinson Hydrogenation
- 10.5 Dynamic NMR
- Rate of Fluxionality
- Ligand Fluxionality
- 10.6 Spin Saturation Transfer
- 10.7 T1 and the Nuclear Overhauser Effect
- T1 and H2 Complexes
- PHIP and SABRE
- Nuclear Overhauser Effect
- 10.8 IR Spectroscopy
- Carbonyls
- Other Ligands
- Band Identification by Isotope Substitution
- Raman Spectroscopy
- 10.9 Crystallography
- Limitations
- 10.10 Electrochemistry and EPR
- 10.11 Computation
- 10.12 Other Methods
- Mass Spectroscopy
- Single-Molecule Imaging
- Interpretation of Results
- References
- Problems
- 11: M-L Multiple Bonds
- 11.1 Carbenes
- Fischer versus Schrock Carbenes
- Fischer Carbenes
- Schrock Carbenes
- Intermediate Cases
- Boryls
- 11.2 Carbynes
- Synthesis
- Structure and Spectra
- Reactions
- 11.3 Bridging Carbenes and Carbynes
- Structure and Spectra
- Reactions
- 11.4 N-Heterocyclic Carbenes
- Synthesis of NHC Complexes.
- Polydentate NHCs
- Applications
- 11.5 Multiple Bonds to Heteroatoms
- Oxo Wall
- Synthesis
- Spectra and Structure
- References
- Problems
- 12: Applications
- 12.1 Alkene Metathesis
- Mechanism
- Selectivity in Cross Metathesis
- Commercial Applications
- 12.2 Dimerization, Oligomerization, and Polymerization of Alkenes
- Catalyst Activation
- Microstructure
- Mechanism
- SHOP Oligomerization
- 12.3 Activation of CO And CO2
- Water-Gas Shift
- Monsanto Acetic Acid Process
- CO2 Activation
- 12.4 C-H Activation
- Shilov Chemistry
- Other Routes
- C-C Bond Formation and Cleavage
- 12.5 Green Chemistry
- Alcohol Activation and Hydrogen Borrowing
- 12.6 Energy Chemistry
- References
- Problems
- 13: Clusters, Nanoparticles, Materials, and Surfaces
- 13.1 Cluster Structures
- Effective Atomic Number (EAN) Rule
- Wade-Mingos Rules
- 13.2 The Isolobal Analogy
- 13.3 Nanoparticles
- 13.4 Organometallic Materials
- Bulk Materials
- Porous Materials
- Metal Organic Frameworks (MOFs)
- Porous Organic Polymers (POPs)
- Organometallic Polymers
- Molecular Wires
- Molecular Electronics
- Nonlinear Optical (NLO) Materials
- Organic Light-Emitting Diodes (OLEDs)
- Sensors
- References
- Problems
- 14: Organic Applications
- 14.1 Carbon-Carbon Coupling
- 14.2 Metathesis
- 14.3 Cyclopropanation And C-H Insertion
- 14.4 Hydrogenation
- Kinetic Resolution
- Asymmetric Hydrogenation
- 14.5 Carbonylation
- 14.6 Oxidation
- 14.7 C-H Activation
- 14.8 Click Chemistry
- References
- Problems
- 15: Paramagnetic and High Oxidation-State Complexes
- 15.1 Magnetism and Spin States
- Spin States
- Influence of Spin State Changes on Kinetics and Thermodynamics
- 3d versus 4d and 5d Metals
- NMR Spectroscopy
- 15.2 Polyalkyls and Polyhydrides
- Group 4
- Group 5
- Group 6
- Group 7
- Groups 8-l0
- Group 11.
- ?7 Ligands
- ?8 Ligands
- 5.6 Isolobal Replacement and Metalacycles
- 5.7 Stability of Polyene and Polyenyl Complexes
- References
- Problems
- 6: Oxidative Addition and Reductive Elimination
- 6.1 Introduction
- 6.2 Concerted Additions
- 6.3 SN2 Pathways
- 6.4 Radical Mechanisms
- 6.5 Ionic Mechanisms
- 6.6 Reductive Elimination
- Octahedral Complexes
- Other Complexes
- Binuclear Reductive Elimination
- Reductive Elimination of C-F, -O, and -N
- 6.7?-Bond Metathesis
- 6.8 Oxidative Coupling and Reductive Fragmentation
- References
- Problems
- 7: Insertion and Elimination
- 7.1 Introduction
- 7.2 CO Insertion
- Enhancing Insertion Rates
- Apparent Insertions
- Double Insertion
- 7.3 Alkene Insertion
- Regiochemistry of Insertion
- Syn versus Apparent Anti Insertion
- Insertion into M-H versus M-R
- Radical Pathways
- Alternating CO/Alkene Insertion
- 7.4 Outer Sphere Insertions
- 7.5?,?,?, And? Elimination
- ? Elimination
- ? Elimination
- Other Eliminations
- References
- Problems
- 8: Addition and Abstraction
- 8.1 Introduction
- 8.2 Nucleophilic Addition to CO
- 8.3 Nucleophilic Addition to Polyenes and Polyenyls
- Davies-Green-Mingos Rules
- Wacker Process
- Alkyne Hydration
- 8.4 Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls
- Hydrides
- Alkyls and Acyls
- 8.5 Electrophilic Addition and Abstraction
- Addition to the Metal
- Addition to a Metal-Ligand Bond
- Addition to Ligand
- Abstraction of Alkyl Groups
- 8.6 Single-Electron Transfer and Radical Reactions
- References
- Problems
- 9: Homogeneous Catalysis
- 9.1 Catalytic Cycles
- Homogeneity
- Thermodynamics
- Kinetics
- Mechanism, Intermediates, and Kinetic Competence
- Cooperative Catalysis
- Deactivation
- Choice of Metal and Ligands
- 9.2 Alkene Isomerization
- Alkyl Mechanism
- Allyl Mechanism.
- Reductive Elimination
- Kinetic Stability from Bulky Substituents
- Preparation of Metal Alkyls
- Cyclometalation
- Oxidative Addition
- Insertion
- Bridging Alkyls
- Metalacycles
- ?1 and?2-Acyl and Vinyls
- 3.2 Other?-Bonded Ligands
- Group 14 Elements
- Groups 15-17
- Oxophilicity and Functional Group Tolerance
- 3.3 Metal Hydrides
- Characterization
- Synthesis
- Reactions
- Hydricity
- Bridging Hydrides
- 3.4 Sigma Complexes
- Dihydrogen Complexes20
- Characterization
- Reactions
- Agostic Species
- 3.5 Bond Strengths
- Supramolecular Interactions
- References
- Problems
- 4: Carbonyls, Phosphines, and Substitution
- 4.1 Metal Carbonyls
- Preparation of Carbonyls
- Reactions of Carbonyls
- Bridging Carbonyls
- Isonitriles
- Thiocarbonyls
- Nitrosyls
- Cyanide
- Other CO Analogs
- 4.2 Phosphines
- Structure and Bonding
- Tolman Electronic Parameter and Cone Angle
- Bite Angle
- 4.3 N-Heterocyclic Carbenes (NHCs)
- 4.4 Dissociative Substitution
- Kinetics
- Stereochemistry and Trans Effect
- Electronic and Steric Factors
- 4.5 Associative Substitution
- Kinetics
- Trans Effect
- Solvent Participation
- Ligand Rearrangements
- 4.6 Redox Effects and Interchange Substitution
- 17e and 19e Species
- The Interchange Mechanism
- 4.7 Photochemical Substitution
- Carbonyls
- Other Photochemical Processes
- 4.8 Counterions and Solvents in Substitution
- "Noncoordinating" Anions
- References
- Problems
- 5: Pi-Complexes
- 5.1 Alkene and Alkyne Complexes
- Synthesis
- Reactions
- Alkyne Complexes
- 5.2 Allyls
- Synthesis
- Reactions
- Related Ligands
- 5.3 Diene Complexes
- Cyclobutadiene Complexes
- Trimethylenemethane
- 5.4 Cyclopentadienyl Complexes
- Bent Metallocenes
- Synthesis
- Cp Analogs
- 5.5 Arenes and Other Alicyclic Ligands
- Synthesis
- Other Arene Ligands.
- Cover
- Title page
- Copyright page
- Contents
- Preface
- List of Abbreviations
- 1: Introduction
- 1.1 Why Study Organometallic Chemistry
- 1.2 Coordination Chemistry
- 1.3 Werner Complexes
- Stereochemistry
- Chelate Effect
- Werner's Coordination Theory
- 1.4 The Trans Effect
- 1.5 Soft versus Hard Ligands
- 1.6 The Crystal Field
- High Spin versus Low Spin
- Inert versus Labile Coordination
- Jahn-Teller Distortion
- Low- versus High-Field Ligands
- Magnetism and Nuclearity
- Other Geometries
- Isoconfigurational Ions
- 1.7 The Ligand Field
- 1.8 The sdn Model and Hypervalency
- 1.9 Back Bonding
- Frontier Orbitals
- ?-Donor Ligands
- 1.10 Electroneutrality
- Oxidation State Trends
- Periodic Trends
- 1.11 Types of Ligand
- Ambidentate Ligands
- Actor and Spectator Ligands
- Multifunctional Ligands29
- Organometallic versus Coordination Compounds
- References
- Problems
- 2: Making Sense of Organometallic Complexes
- 2.1 The 18-Electron Rule
- Covalent Electron Counting Model
- Ionic Electron Counting Model
- Electron Counts for Common Ligands and Hapticity
- Bridging Ligands
- Zero-Electron Ligands
- 2.2 Limitations of The 18-Electron Rule
- Steric Stabilization of Reactive Species
- 2.3 Electron Counting in Reactions
- 2.4 Oxidation State
- Oxidation State versus Real Charge
- Ambiguous Oxidation States and Noninnocent Ligands
- Maximum and Minimum Oxidation States
- Net Ionic Charge
- 2.5 Coordination Number and Geometry
- 2.6 Effects of Complexation
- Ligand Polarization
- Free ≠ Bound
- Symbiotic and Antisymbiotic Effects
- 2.7 Differences between Metals
- Real Charge
- References
- Problems
- 3: Alkyls and Hydrides
- 3.1 Alkyls and Aryls
- Metal Alkyls as Stabilized Carbanions
- ? Elimination
- Stable Alkyls
- Agostic Alkyls
- ? Elimination of Other Groups.